Removal of a



United States Patent Ce 1 2,734,892 REMOVAL OF AlCls CATALYST FROMFRIEDEL- CRAFTS REACTION MASSES Richard Pence Carter, Beverly, N. J.,assignor to Hercules Powder Company, Wilmington, Del., a corporation ofDelaware No Drawing. Application September 10, 1952, Serial No. 308,94712 Claims. (Cl. 260-935) This invention relates to Alcls-catalyzedFriedel-Crafts reactions, and more particularly, it relates toAlCls-catalyzed Friedel-Crafts reactions of the type involvingpolymerization. Still more particularly, it relates to a process for theinactivation and removal of AlCls catalyst from the reaction massesobtained in AlCls-catalyzed Friedel- Crafts reactions.

The original observationsof Friedel and Crafts related to the reactioninvolving the replacement of hydrogen in an aliphatic compound, amylchloride. The reaction was effected in the presence of AlCls ascatalyst. The specific reaction referred to may be illustrated asfollows:

A1Cl aHnCl CsHnCl CioHnCl HCl Following this early work, it was foundthat a variety of other metal halides were similar to AlCl3 in having acatalytic effect on this reaction. Thus, the halides of aluminum, iron,zinc, boron, tin, titanium, bismuth, antimony, etc. were found to beeflective. At the same time it was found that these catalysts possessedcatalytic activity not only with respect to the above alkylationreaction but with respect to a rather wide variety of other reactions.Reactions made possible through the catalytic intervention of metalhalides permit the synthesis of a great many compounds. Some of the moreimportant of these reactions are the following: alkylation reactions,synthesis of ketones, preparation of carboxylic acid derivatives,aldehyde synthesis, preparation of primary and secondary amines,preparation of halogeno compounds, dehydration reactions, isomerizationreactions, polymerization reactions, etc. The technical and patentliterature tends to associate these diverse developments with theoriginal work of Friedel and Crafts and the term Friedel-Crafts reactionhas been expanded in scope with each new addition to the field of use ofthe metal halide catalysts. It is in this expanded or broad sense thatthe term is used herein.

It is the polymerization-type of Friedel-Crafts reaction which is ofparticular interest so far as this invention is concerned. As an exampleof this type there may be mentioned the polymerization of terpenes andcopolymerization of terpenes and other unsaturated organic compounds inthe presence of a Friedel-Crafts catalyst. Such reactions are generallycarried out with the terpene or mixture thereof with an unsaturatedorganic compound dissolved in an unreactive solvent although the use ofsuch unreactive solvent is not entirely necessary.

In this manner, it is possible to make hard resins and a a variety ofoils, some of which have drying characteristics. Products intermediatein physical characteristics between hard resins and drying oils are alsoobtainable. Of all the Friedel-Crafts catalysts, AlCls is preferablyused as the polymerization catalys for this type of polymerization. Thereason for this reference lies'in the fact that AlCl3 is a particularlystrong catalyst for this type of polymerization.

In the recovery of the polymeric constituents from the polymerizationreaction mass or in the recovery of, the

desired product from any Friedel-Crafts reaction mass whether or not itis derived from a polymerization type reaction, it is necessary toremove the AlCla. Actually, this compound is believed to be present inthe reaction Patented Feb. 14, 1956' mass in the form of an organiccomplex which must be decomposed and the inorganic material removed. Oneof the prior art procedures for eifecting this is to wash the reactionmass with water, an aqueous acid or an aqueous base. U. S. 2,335,912; U.S. 2,391,293; and U. S. 1,938,320 describe a purification treatment ofthis type. Another procedure involves the use of an alcoholic ethylalcohol forms an inactive organic complex with anhydrous AlCl3. Withrespect to prior art procedures generally, it is difficult to obtain aproduct, whether it be a polymer, alkylation product, or other typeproduct, which has at the same time a low inorganic content and a verylight color.

The use of Ca(OH)2 as a precipitant for the AlCla catalyst in reactionmasses obtained in Friedel-Crafts reactions generally gives a gelatinousprecipitate (apparently Al(OH)3) which is exceedingly difiicult if notimpossible to remove. Under such conditions it is not possible to removeAlCls completely from the reaction mixture. However, I have foundfurther that, if a controlled amount of water is added to such areaction mass in conjunction with the Ca(OH)z, an easily filterableprecipitate is formed and that by using the proper proportions ofCa(OH)2 and water substantially complete removal of the AlCls catalystcan be effected in this way. The precipitate obtained is apparently amixture or complex of Al(OH)3 and one or more hydrates of the CaClzformed by neutralization with Ca(OH)z of the HCl resulting fromhydrolysis of the AlCls. CaClz is known to form a mono-, di-, andhexahydrate, and it may form still others. Mg(OH)2 is equivalent toCa(OH)2 in this application and its chloride MgClz is also known to formthe same hydrates. As would be expected, the corresponding oxides may beused, CaO and MgQ.

Thus, in accordance with this invention, a Friedel- Crafts hydrocarbonsynthesis is carried out using a procedure known to the art for theparticular type of Friedel-Crafts reaction involved. The desiredreactant or reactants, which may be hydrocarbons or halogenatedhydrocarbons, are contacted with anhydrous AlCl3 as catalyst for aperiod of time sufiicient to effect at least a substantial amount of thedesired reaction. The reaction is preferably, although not necessarily,carried out with the reactant or reactants dissolved in an unreactiveorganic solvent. At the end of the reaction step, there is added to thereaction mass and thoroughly mixed therewith a limited amount of waterand a limited amount of an alkaline material. The alkaline material usedis preferably CaO or Ca(OH)z although MgO or Mg(OH)2 may be employed, ifdesired. A precipitate forms which is believed to be Al(OH)3 and one ormore of the hydrates of CaClz or MgClz depending upon whether a calciumor magnesium compound has been used for the precipitation. Theprecipitate is then removed from the reaction mass by some suitablemethod as filtration, etc. Thereafter, the desired constituents of thereaction mass, for example, the polymeric constituents in the case of apolymerization-type reaction, are recovered therefrom in accordance withknown procedures.

As stated above, a limited amount of alkaline material, i. e., CaO,Ca(OH)2, MgO, .Mg(OH)2, is used to effect the precipitation. It has beenfound that a minimum of 1.5 moles of alkaline material per mole of AlCl3employed originally is required to effect a substantially completeremoval of the AlCls. Although 1.5 moles of the alkaline material isefiective, it is much preferred to employ from 3.6 to 4.5 moles ofalkaline material per mole of AlCls. If an amount of alkaline materialin the preferred range is employed, the precipitate formed is easilyfiltered. There is some tendency, if less than the preferred proportionsare employed, for the precipitate to occlude the desired constituents ofthe reaction mass, thereby reducing the yield of the desiredconstituents. While more than 4.5 moles of alkaline material per mole ofAlCls may be employed, there is no particular advantage in using suchexcessive amounts. The proportions of water employed in theprecipitation are critical. The water is employed in such an amount asto provide the water required to hydrate any oxide employed as alkalinematerial and to provide additionally from 0.75 to 15 moles of water permole of AlCla. It is preferred to employ from 1.5 to 7.5 moles of waterper mole of AlCls in addition to that required to hydrate any oxideemployed.

The process herein described is very satisfactory and.

provides numerous advantages over processes actually in commercial useand those which have been merely suggested in the literature. Thisprocess avoids the inherent difliculty of emulsification connected withany water, aqueous acid, or aqueous base washing step. Comparativelyspeaking, by using the subject process for removal of AlCla, it is mucheasier to obtain products having a low inorganic content and light coloras compared with the prior art process involving use of a water, aqueousacid, or aqueous base washing step. In accordance with the newlydiscovered process, another desirable feature resides in the fact thatthe reaction mass is substantially anhydrous after removal of theprecipitate and hence it is practically free of inorganic matter. It isonly necessary to remove the solvent if any has been employed and tofractionate the remaining material. For example, in the case of apolymerization reaction mass, after removal of catalyst and solvent, ifany, the remaining material is fractionated to separate the polymersfrom the monomers. As compared with the prior art process usingalcoholic NH3, the newly discovered process is advantageous in that itdoes not provide a solvent contaminated with ethyl alcohol. As pointedout above, ethyl alcohol tends to form an inactive organic complex withAlCls; hence, its presence must be avoided during the polymerizationstep.

While this invention is broad in its application, it is not applicableto all Friedel-Crafts reaction masses. It is applicable to allFriedel-Crafts hydrocarbon syntheses, which reactions includealkylation, isomerization, polymerization, dehydration anddehydrohalogenation reactions. Friedel-Crafts hydrocarbon syntheses maybe further characterized by the fact that all the organic reagentsinvolved in such reactions are hydrocarbons or halogenated hydrocarbonsand it may therefore be said that the present invention is a process forinactivating and removing AlCl3 catalyst from a solution of the g .4.reaction product produced by an AlCls-catalyzed Friedel- Crafts reactionwherein all the organic reactants are hydrocarbons or halogenatedhydrocarbons. In general,

.this invention cannot be employed in connection with Friedel-Craftsreactions wherein oxygen-containing materials are found as. for example,in ketone syntheses.

The invention is particularly applicable to reaction masses obtained inFriedel-Crafts polymerization reactions. For that'reason and for ease ofpresentation the invention will be described in relation to'thatparticular type of Friedel-Crafts reaction. It will be understood,however, that the invention has broader significance as indicatedhereinabove.

Having described the generic aspects of this invention, the followingspecific examples are given as specific -em-, bodiments thereof. Thesespecific examples should not be construed as limiting the invention inanyway. ,All parts and percentages are by weight unless otherwiseindicated.

EXAMPLE 1 To 5000 parts of benzene in a round bottom flask equipped foragitation was added 200 parts of anhydrous AlCla and the suspensioncooled in an ice bath to 5 to 10 C. A 2500 part sample of unrefinedsulfateturpentine (analyzing 05% S with a strong odor of organic sul-.fide) was added to the benzene suspension with agitation at such a rateas to keep the reaction temperature at 5 to 10 C. while cooling in anice bath. About 2.5 hours were required for this addition. The resultingsolution was agitated at 0 to 5 C. for 4 hours after the turpentine hadbeen completely added. At the end of the 4-hour period, 453 parts ofCa(OH)z and 104 parts of water were added to the reaction mass. Theresulting suspension was rapidly agitated at C. In about 10 minutes thedark purple-red color changed to light yellow indicating decompositionof the catalyst. The reaction mass was stirred for 30 minutes after thiscolor change and finally filtered with suction. The filtration wasaccomplished easily in a period of about 15 minutes. The sol vent andunreacted constituents were removed from the filtrate by distillationusing a final temperature of 220 C.

at 20 mm. pressure. The resulting product was a resin having no organicsulfide odor. It had the following characteristics; color, M+ (U. S.Rosin Grade); softening point (drop). 72 C.; S; 0.03%; Cl, 0.6%; and ash(as sulfates), 0.005%. Two thousand one hundred twenty parts of resinwas obtained by this procedure, amounting to a yield of 84+%.

Several additional examples were carried out in which sulfate turpentinewas polymerized in benzene solution using AlCl3 as catalyst. The percent catalyst based on the turpentine was 8% in all cases except inExample .5 where it was 10%. The conditions of the examples were thesame as those of Example 1 except as shown to be different in Table I.In this table there are summarized data relating to conditions ofreaction andthe results obtained;

I Table I Time Re- Drop Temp. qmred to Yield, Soften- Exomple TerpeneA1015 Ca(OH)z Water 1 o (l rilnlcge Percent imiPoint Color (minutes)Steam-distilled Unrefined Sul- 8 18 4. 5 60 15 91 77 X3 fate Turpentine3 d0 8 20 1.6 ,80 10 87 ,WG do 8 20 8.6 25 10 7 01 70 K DistilledSulfate Turpentine 10 10 6. 5 60 30 84 74 X Refined Sulfate Turpentine-453 104 6G 15 86 56 N 1 Temp. during precipitation step. 3 Parts byweight.

5 Unrefmed sulfate turpentine steam-distilled from aqueous base.

4 Reflux temperature.

7 Calesst an 10 p. p. m. and not detected; Al less than 5 p. pjm. but;detected. 7

Several additional examples were carried outin which various terpeneswere polymerized in benzene solution using AlCla as catalyst. The percent catalyst based on the terpene was 5% in all cases except in Example7 Where it was The conditions of the examples were AlCls. As exemplaryof the prior art, menti 11 may be made of U. S. 1,938,320 which relatesto the polymerization of pine extracts such as pine oil, dipentene,sylvestrene, turpentine, etc. in the presence of AlCl3. Similarly, U. S.1,939,932 shows the polymerization of pinene, di-

the same as those of Example lexcept as shown to be 5 pentene,turpentine, cedar oil, limonene, etc. in the presditferent in Table II.In this table there are summarized ence of A1013. U. 8. 2,264,774 issignificant in that it data relating to conditions of reaction and theresults shows that both a-piene and fi-piene polymerize in thepresobtained. ence of A1Cl3.

Table 11 Time Re- Drop Temp. 2 quued to Yield Soften- Example TerpeneA101; Ca(0H)1 Water 0 0' relnfive Percefit 0 Point Color (minutes) Resingrade Dipeutene 10 22.5 4.0 so 10 70 61 M Pure Dipentene 125 500 50.0 509a 111 Y do 2.5 15.0 1.0 70 10 94 125 Y Pure B-Pinene 10 22.5 ;4.0 V 601o 94 145 x 1 Parts by weight. 2 Temp. during precipitation step. 3Toluene used instead of benzene as solvent for the reaction.

Several additional examples were carried out in which i U. S.2,335,912'relates particularly to the polymerizaterpenes werecopolymerized with other unsaturated ma- 5 tion of fl-piene or aft-piene terpene fraction containing terials in benzene solution usingAlCls as catalyst. The [3-piene in excess of 50% of the terpene presentin the per cent catalyst based on the terpene was 5% in all presence ofa metalhalide as catalyst; Terpinene and cases except in Example 13where it was 10%. The terpinolene are also shown to undergopolymerization in conditions of the examples were the same as those ofthe presence of a metal halide catalyst although the reac- Example 1except as shown to be different in Table III. tion in each of thesecases is much less vigorous than in In this table there are summarizeddata relating to conthe case of p-piene. The polymerization ofturpentine ditions of reaction and the results obtained. in the presenceof a metal halide catalyst under condi- Table 111 Time Re- Drop qmred toExample Terpene AlCh Ga(OH)2 Water g gf" manage 232 31 Color (minutes)11 Pure Dipentene-Butadlene 5 30 4.0 10 93 175 WG Mixturefi, PurePipentene-Styrene Mix- 10 22 4.0 10 95 135 WG ture. SulfateTurpentine-Coumarone 8 18 4.5 60 16 91.3 78 X:

Indene Mixture.

1 Parts by weight.

2 Temp. durin recipitation step.

? Contained 15 0 butadiene.

4 Ethyl chloride used as solvent for the reaction. I

' Benzene added to replace ethyl chloride lost by evaporation.

! Contained 15% styrene.

Contained 15% distilled solvent naphtha (63% polymerizable with Gene.H1804).

Based on polymerizable constituents. I

The examples have illustrated the application of the invention to thepreparation of various specific terpene polymers and copolymers. Asindicated previously, the invention has much broader application.Considering polymerization reactions only, the invention may be appliedto any reaction mass obtained as a result of an AlCls-catalyzedFriedel-Crafts polymerization reaction. Thus, the polymerization ofolefins such as ethylene, propene, butene-l, butene-2, isobutene, etc.in the presence of AlCla comes within the orbit of the invention. Thepolymerization of diolefins such as butadiene-1,3, isoprene, etc. isincluded. Similarly, the copolymerization of diolefins with olefins inthe presence of AlCla is included. Examples of such copolymerization arecopolymerization of cyclohexene and isoprene, copolymerization ofcyclohexadiene and pentene-2, etc. Similarly, the polymerization ofaromatic unsaturated compounds is included. For example, thepolymerization of styrene, indene, etc. in the presence of AiCls isincluded.

The invention may be applied to the preparation of polymers from anyterpene having the empirical formula C10H1s. It is well known to the artthat terpenes having this formula undergo polymerization in the presenceof a Friedel-Crafts catalyst, specifically in the presence of tions toobtain an exceptionally high yield of solid polymer is the subject of U.S. 2,391,293.

The above-mentioned patents and the specific examples included in thisapplication have related particularly to cyclic terpenes of the formulaC10H16 and the polymerization thereof. tion has application to thepolymerization of acyclic terpenes such as allo-ocirnene, myrcene, etc.as well as to the polymerization of the cyclic terpenes. In thisconnection it is pertinent to mention U. S. 2,373,419 which disclosesthat useful polymers can be made from allo-ocimene, myrcene, etc. bytreatment thereof with a metal halide catalyst such as AlCle.

It will be apparent from a study of the aforementioned patent art thatmixtures of terpenes may be utilized to form desirable polymers whetherthey be of the hard resin type, the oil type, or the types which areintermediate in physical properties. Thus, gum turpentine may beemployed as a starting material. This material is said to have anaverage composition of 70% u-pinene and 30% ,B-pinene. Similarly, woodturpentine which contains a proportionately smaller amount of ,B-pinenemay be used as a starting material. The subject invention is applicableto the use of any such mixtures of terpenes in the preparation ofpolymers therefrom.

It is pointed out, however, that this inven- Special mention may be madeof the application of the invention to polymers made from sulfateturpentine, sul fate turpentine being the turpentine obtained as abyproduct in the pulping of wood by the so-called sulfate process.Sulfate turpentine in its unrefined form characteristically has a strongodor of organic sulfur compounds. Furthermore, as compared with regularwood or gum turpentine, it is comparatively dark in color. Aparticularly desirable feature of the present invention is that startingwith an unrefined sulfate turpentine, it is possible by the applicationof the technique of this invention to produce a resinous polymer whichis not only substantially free of inorganic material but which isentirely free of the odor of organic sulfur compounds and is light incolor. Thus, it is possible to start with a relatively crude unrefinedmaterial and obtain a polymerized form thereof which is refined withrespect to odor and color.

Similarly, this invention has application to the preparation ofcopolymers from any of the terpenes having the formula CioHis mentionedhereinabove with any unsaturated organic compound copolymerizabletherewith. In this connection, mention may again be made of U. S.1,939,932 which discloses the copolymerization of terpenes and coumaroneor indene or cournarone/ indene mixtures in the presence of AlCls. U. S.2,287,535 has a similar disclosure in this respect.

The copolymerization of a terpene hydrocarbon of the formula Ciel-11sand a halide of an unsaturated hydrocarbon is the subject of U. S.2,354,775. As examples of such halides, vinyl chloride, vinyl bromide,vinylidene chloride, etc. are named. The copolymerization of terpenehydrocarbons of the formula CioHie and 1,3-butadiene or a derivativethereof is the subject of application Serial No. 614,432 filed September4,. 1945, by A. L. Rummelsburg, now Patent No. 2,487,898. German Patent278,468 is of some significance in that it shows the copolymerization ofterpenes and styrene in the presence of AlCls. Other pertinent patentsare U. S. 2,370,- 068 and U. S. 2,354,776 which relate to the copolymersof a terpene hydrocarbon and a glyceryl ester of an unsaturated fattyacid and to copolymers of a terpene hydrocarbon and a rosin ester,respectively.

The purification or catalyst-removing operation to which this inventionis particularly directed may be applied to any polymerization reactionmass regardless of whether or not the polymerization has been eifectedwith the monomer or monomers dissolved in an inert solvent. It ispreferred, however, that the polymerization be carried out in thepresence of an inert solvent since the presence of the solvent has someeffect on the efliciency of the purification treatment, and inparticular it is preferred to employ an aromatic hydrocarbon such asbenzene, toluene, xylene, solvent naphtha, etc., or a halogenatedhydrocarbon such as ethyl chloride, ethylene dichloride, sym.tetrachloroethane, o-dichlorobenzene, etc. as solvents. inert solventsother than the preferred classes of solvents just mentioned may, ofcourse, be employed. Thus, for example, gasoline, petroleum ether, V. M.& P. naphtha, etc. may be employed.

In precipitating the AlCls catalyst it matters not whether the alkalinematerial (Ca(OH)2) is added first or the water added first. Furthermore,it is quite satisfactory to make a paste of the two and add that to thereaction mass. Whichever procedure is employed, it is important tothoroughly mix the reaction mass after addition to insure substantiallycomplete removal of the AlCls.

In general, it may be said that almost any temperature may be employedin carrying out the removal of AlCls. From a practical standpoint thatmeans that any temperature from C. up to the temperatures ofdecomposition of the reaction mass may be employed. From the standpointof achieving rapid removal of the catalyst, however, it is helpful toknow that the minimum temperature at which rapid removal of the catalystis efiected variesinversely with the mols of water added to the reactionmass per mol of AlCl3 catalyst. Thus, at 0.75 to 1.5 mols of water permolof AlCla a temperature of at least C. is required to give rapidremoval of the catalyst. At 4.1 mols of water per mol of AlCls, atemperature of 60 C. or more is required to give rapid removal of thecatalyst. At 7.5-15 mols of water per mol of AlCl3, rapid removal of thecatalyst can be effected at room temperature. It has been mentionedheretofore that the preferred amount of water to employ per mol of AlClsis from 1.5 mols to 7.5 mols. In conjunction with operations within thisrange a temperature of 25 to 80 C. should be employed to obtainreasonably rapid removal of catalyst.

As indicated previously, an amount of water substantially in excess of15 mols of water per mol of AlCls cannot be used in accordance with theinvention. Such practice gives rise to a reaction mass which is notanhy-- drous. Consequently, the polymer isolated therefrom will have ahigh inorganic content which is undesirable.

Looking at the matter from a theoretical standpoint,

since the highest known hydrates of CaClz or MgClz are those involving 6molecules of water, it would appear that 9 mols of water per mol ofAlCls would be the maximum amount of water which could be added Whileretaining an anhydrous condition in the reaction mass. Practically,however, that limitation is not applicable. It appears that CaClz.6H2Oor the corresponding MgCl2.6H2O are hydroscopic enough to keep theresulting reaction mass substantially anhydrous up to the point where 15'mols of water have been added per mol of AlCls.

Although the examples herein have illustrated only the separation of theprecipitate by filtration, there are numerous obvious expedients whichcan be employed in place thereof such as, for example, centrifugation,settling and decanting, etc.

This application is a continuation-in-part of application Serial No.136,431, filed December 31, 1949, now abandoned.

What I claim and desire to protect by Letters Patent is:

1. A process for the removal of AlCls catalyst from a reaction massproduced by an AlCls-catalyzed Friedel- Crafts polymerization reactionwherein all of the organic reactants are selected from the groupconsisting of ethylenically unsaturated hydrocarbons and halogenatedhydrocarbons which comprises adding to said reaction mass an alkalinematerial selected from the group consisting of CaO, Ca(OI-I)2, MgO andMg(OH)z, and a liquid consisting of water; agitating the resultingmixture; and removing the resulting precipitate, said alkaline materialbeing employed in an amount of at least 1.5 mole per mole of AlClspresent and said water being employed in excess of the amount of waternecessary to hydrate any oxide employed as alkaline material, saidexcess being in an amount of from about 0.75 to 15 moles of water permole of AlCls present.

2. The process of claim 1 in which the reaction mass is produced by anAlCls-catalyzed Friedel-Crafts polymerization reaction in which theorganic reactant is an ethylenically unsaturated hydrocarbon.

3. The process of claim 2 wherein the polymerization reaction is acopolymerizati'on reaction between a terpene and an ethylenicallyunsaturated compound.

4. The process of claim 2 wherein the ethylenically unsaturated monomeris a terpene.

5. The process of claim 4 wherein Ca(OH)2 is employed as the alkalinematerial.

6. The process of claim 4 wherein the alkaline material is employed inthe amount of from about 3.6 to 4.5 moles per mole of AlCls.

7. The process of claim 6 wherein the water is employed in excess of theamount of water necessary to hydrate any oxide employed as alkalinematerial, said excess being in an amount of from about 1.5 to 7.5 molesof water per mole of AlCls present.

8. The process of claim 7 wherein Ca(OH)2 is employed as the alkalinematerial.

9. The process of claim 2 is produced by an AlCls-catalyzedFriedel-Crafts polymerization of sulfate turpentine.

10. The process of claim 9 in which the alkaline material is employed inthe amount of from about 3.6 to 4.5 moles per mole of AlCls and theexcess of Water is in an amount of from about 1.5 to 7.5 moles of waterper mole of AlCl3 present.

in which the reaction mass 5 10 11. The process of claim 2 in which thereaction mass is produced by an AlCla-catalyzed Friedel-Craftspolymerization of p-pinene.

12. The process of claim 2 in which the reaction mass is produced by anAlCls-catalyzed Friedel-Crafts polymerization of dipentene.

References Cited in the file of this patent UNITED STATES PATENTS

1. A PROCESS FOR THE REMOVAL OF ALCL3 CATALYST FROM A REACTION MASSPRODUCED BY AN ALCL3-CATALYZED FRIEDELCRAFTS POLYMERIZATION REACTIONWHEREIN ALL OF THE ORGANIC REACTANTS ARE SELECTED FROM THE GROUPCONSISTING OF ETHYLENICALLY UNSATURATED HYDROCARBONS AND HALOGENATEDHYDROCARBONS WHICH COMPRISES ADDING TO SAID REACTION MASS AN ALKALINEMATERIAL SELECTED FROM THE GROUP CONSISTING OF CAO, CA(OH)2, MGO ANDMG(OH)2, AND A LIQUID CONSISTING OF WATER; AGITATING THE RESULTINGMIXTURE, AND REMOVING THE RESULTING PRECIPITATE, SAID ALKALINE MATERIALBEING EMPOLOYED IN AN AMOUNT OF AT LEAST 1.5 MOLE PER MOLE OF ALCL3PRESENT AND SAID WATER BEING EMPLOYED IN EXCESS OF THE AMOUNT OF WATERNECESSARY TO HYDRATE ANY OXIDE EMPLOYED AS ALKALINE MATERIAL, SAIDEXCESS BEING IN AN AMOUNT FROM ABOUT 0.75 TO 15 MOLES OF WATER PER MOLEOF ALC3 PRESENT.